NOVEL METAL-CONTAINING ZEOLITE BETA FOR NOx REDUCTION AND METHODS OF MAKING THE SAME

ABSTRACT

There is disclosed an organic-free, metal-containing zeolite Beta with a silica-to-alumina ratio (SAR) ranging from 5 and 20, and a metal content of at least 0.5 wt. %. There is also disclosed a method of making such a zeolite Beta without organic structure directing agent (SDA). The metal, which may comprise Fe or Cu, can be found in amounts ranging from 1-10 wt. %. A method of selective catalytic reduction of nitrogen oxides in exhaust gases using the disclosed zeolite is also disclosed.

This application claims the benefit of domestic priority to U.S.Provisional Patent Application No. 61/347,210, filed May 21, 2010, whichis herein incorporated by reference in its entirety.

The present disclosure relates to a metal-containing zeolite Beta andmethods of making the same. The present disclosure also relates tomethods of using such zeolites, including for selective catalyticreduction (SCR) of nitrogen oxides (NO_(x)) in exhaust gases.

Nitric oxides (NO_(x)) have long been known to be polluting gases,principally by reason of their corrosive action. In fact, they are theprimary reason for the cause of acid rain. A major contributor ofpollution by NO_(x)s is their emission in the exhaust gases of dieselautomobiles and stationary sources such as coal-fired power plants andturbines. To avoid these harmful emissions, SCR is employed and involvesthe use of zeolitic catalysts in converting NO_(x) to nitrogen andwater.

The following patents disclose the use of zeolites or similar catalyticmaterials, and are herein incorporated by reference: U.S. Pat. No.4,952,385; U.S. Pat. No. 4,961,917; U.S. Pat. No. 5,451,387; U.S. Pat.No. 6,689,709; U.S. Pat. No. 7,118,722; U.S. Pat. No. 6,890,501.

In general, the synthesis of zeolites, particularly Beta zeolite, occursin the presence of organic templates, which are known in the art asstructure directing agents (SDAs). One common SDA that is typically usedto synthesize Beta zeolite is tetraethylammonium hydroxide (TEAOH).However, the drawbacks associated with the use of such SDAs, includingin increased material costs, increased processing steps, and adverseeffect on environment, make it desirable to develop a process ofsynthesizing zeolites, such as Beta zeolite, without the use of organicSDAs.

Synthesis of organic-free zeolite Beta was known in the art. See, forexample, B. Xie, J. Song, L. Ren, Y. Ji, J. Li, F.-S. Xiao, Chemistry ofMaterials, 2008, 20, 4533, and G. Majano, L. Delmotte, V. Valtchev, S.Mintova, Chemistry of Materials, 2009, 21, 4184, both of which areincorporated by reference in their entireties. Neither of thesereferences, however, disclose the claimed method of making a metalcontaining zeolite Beta, and certainly not one used for selectivecatalytic reduction of NO_(x). Thus, there is a need for synthesizingorganic-free zeolite Beta, further comprising a metal and that allowsfor the selective catalytic reduction of NO_(x) in exhaust gases. As aresult, the finished Fe-Beta product is superior to any previousdisclosed Fe-zeolites in Fe-dispersion and selective catalytic reductionactivity.

SUMMARY

Thus, there is disclosed an organic-free metal-containing zeolite Betawith silica-to-alumina ratio (SAR) ranging from 5 and 20, and a methodof making it. The Beta zeolite described herein is synthesized withoutany direct use of an organic structure directing agent (SDA). Thus, theresulting zeolite Beta has no organic template material in its crystalstructure at any point during processing, excluding any residual amountresulting from the seeding materials. In one embodiment, the method ofmaking zeolite Beta according to the present disclosure has silicautilization of greater than 30 percent from the synthesis mixture, suchas a silica utilization of greater than 40 percent, or even greater than50 percent.

In one embodiment, the metal comprises iron (Fe) or copper (Cu) in anamount of at least 0.5 wt. %, such as in an amount ranging from 1-10 wt.%.

In one embodiment, the metal-containing zeolite Beta described hereinexhibits a NO_(x) conversion of at least 40% at 200° C. after beingsteamed at 700° C. for 16 h in 10% steam with balance air.

There is also disclosed a method of selective catalytic reduction ofnitrogen oxides in exhaust gases using the zeolite Beta describedherein. In one embodiment, the method comprises at least partiallycontacting the exhaust gases with a metal-containing zeolite Beta withSAR ranging from 5 and 20 and metal, such as iron or copper, in anamount of at least 0.5 wt %, such as from 1-10 wt. %.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures are incorporated in, and constitute a part ofthis specification.

FIG. 1 is a graph showing NO conversion on Fe-Beta materials steamed at700° C. for 16 h in 10% steam with balance air, on a sample according tothe present disclosure and a comparative sample.

FIG. 2 is an X-ray diffraction pattern of Example 1.

FIG. 3 is an X-ray diffraction pattern of Example 3.

FIG. 4 is an X-ray diffraction pattern of Example 4.

FIG. 5 is a Scanning Electron Microscope image of the material ofExample 1.

FIG. 6 is a Scanning Electron Microscope image of the material ofExample 3.

FIG. 7 is a Scanning Electron Microscope image of the material ofExample 4.

FIG. 8 is a graph showing NH₃—SCR activity of Fe-exchanged zeolite Betaand mordenite samples [Steaming: 700° C. for 16 h in 10% steam/air, SCR:500 ppm NO, 500 ppm NH₃, 5% O₂, balance inert, SV: 60000 h⁻¹].

FIG. 9 is a graph showing NH₃—SCR activity of Example 4 exchanged withvarious amounts of Fe [Steaming: 700° C. for 16 h in 10% steam/air, SCR:500 ppm NO, 500 ppm NH₃, 5% O₂, balance inert, SV: 60000 h⁻¹].

FIG. 10 is a graph showing NH₃—SCR activity of fresh Fe-exchangedzeolite Beta, mordenite, and Y samples [SCR: 500 ppm NO, 500 ppm NH₃, 5%O₂, balance inert, SV: 60000 h⁻¹].

FIG. 11 is a graph showing NH₃—SCR activity of fresh and steamed Cu-Beta[Steaming: 700° C. for 16 h in 10% steam/air; SCR: 500 ppm NO, 500 ppmNH₃, 5% O₂, balance inert, SV: 60000 h⁻¹].

FIG. 12 is a graph showing UV data of Fe-exchanged zeolite Beta samplesthat were treated under the following conditions prior to recording thespectrum: steaming at 700° C. for 16 h in 10% steam/air; dehydrated insitu to 400° C., followed by cooling down to ambient temperature.

FIG. 13 is a graph showing UV data of Example 4 exchanged with variousamounts of Fe. Prior to recording the spectrum, the material was treatedas follows: steaming at 700° C. for 16 h in 10% steam/air; dehydrated insitu to 400° C., followed by cooling down to ambient temperature.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Organic-free,” refers to a method of making Beta zeolite without thedirect use of organic templates, such as organic structure directingagent (SDA), during synthesis. However, it is appreciated that when aseeding material is used, such as a pure Beta zeolite, the seedingmaterial may have been made with or without an SDA. Thus, this termrefers to fact that the resulting Beta product has never been in directcontact with an organic structure directing agent (SDA) during anyprocessing step, but that a seed material may have been made using anSDA, providing, at most, residual or secondary contact with the porestructure. In one embodiment, the resulting Beta zeolite, even ifexposed to residual or secondary contact with an SDA, would not requireone or more post-synthesis treatment steps to open the porous volume ofthe crystalline framework.

“Silica utilization” refers to the efficiency at which silica is used inthe synthesis of zeolite Beta. Silica utilization can be calculated bydividing the silica-to-alumina ratio (SAR) of the product to the SAR ofthe synthesis mixture excluding the seeding material.

“Hydrothermally stable” means having the ability to retain a certainpercentage of initial surface area and/or microporous volume afterexposure to elevated temperature and/or humidity conditions (compared toroom temperature) for a certain period of time.

“Initial Surface Area” means the surface area of the freshly madecrystalline material before exposing it to any aging conditions.

“Initial Micropore Volume” means the micropore volume of the freshlymade crystalline material before exposing it to any aging conditions.

“Direct synthesis” (or any version thereof) refers to a method that doesnot require a metal-doping process after the zeolite has been formed,such as a subsequent ion-exchange or impregnation method.

“Ion Exchange,” refers to exchanging non-framework ionic elements and/ormolecules contained in zeolitic materials with other elements and/ormolecules, such as metals. In general, almost any conceivable elementcan be used in the ion exchange step, including at least one elementselected from the following group: Cu, Fe, Co, Cr, Ni, V, and Nb,preferably Cu and Fe.

“Defined by the Structure Commission of the International ZeoliteAssociation,” is intended to mean those structures included but notlimited to, the structures described in “Atlas of Zeolite FrameworkTypes,” ed. Baerlocher et al., Sixth Revised Edition (Elsevier 2007),which is herein incorporated by reference in its entirety.

“Selective Catalytic Reduction” or “SCR” refers to the reduction ofNO_(x) (typically with ammonia) in the presence of oxygen to formnitrogen and H₂O.

“Exhaust gas” refers to any waste gas formed in an industrial process oroperation and by internal combustion engines, such as from any form ofmotor vehicle.

The unique pore structure associated with crystalline microporousaluminosilicates, such as zeolites, have led to their successful uses ina wide variety of applications, including as catalysts, adsorbents, andion-exchangers. In particular, the combination of its unique threedimensional, 12-ring channel system, and it's high thermal stability,has made Beta zeolite one of the most important industrial zeolites.Traditionally, this zeolite was prepared from precursor materialscontaining organic structure directing agents (SDAs). The SDAs typicallyused to prepare Beta zeolite (such as TEAOH anddibenzyl-dimethylammonium hydroxide) are not only expensive, but theyinevitably are encapsulated in the zeolitic framework, such that aremoval step, e.g. heat treating, is required for their removal. Inaddition, when organic SDAs are used to prepare Beta zeolite, highsilica products are typically obtained. For example, the typical SAR ofsynthetic Beta zeolite is over 20, often over 40.

According to the present invention it has been found that a metalcontaining Beta zeolite can be produced without using an organicstructure directing agent (SDA). By avoiding the use of an organictemplate, the resulting Beta zeolite does not have unwanted organicmaterials in the crystalline material. As a result, one or morepost-synthetic treatments such as calcination for removing SDAs from thecrystallized material is unnecessary.

Thus, there is disclosed a metal-containing zeolite Beta that has neverbeen in contact with an organic structure directing agent (SDA) and amethod of making the same. In one embodiment, the zeolite Beta has a SARranging from 5 to 20, preferably not more than 12, such as a range from5 to 11.

In one embodiment, the zeolite Beta disclosed herein has crystal sizegreater than 0.1 microns, such as a crystal size ranging from 0.2 to 5microns.

In one embodiment, the metal portion of the zeolite Beta comprisescopper or iron, which can be introduced into the zeolite Beta in variousways, such as by liquid-phase, or solid ion-exchange, or impregnation,or incorporated by direct-synthesis. In one embodiment, the metalportion comprises at least 1.0 weight percent of the total weight of thematerial, such as a range from 1.0-10.0 weight percent of the totalweight of the material.

In one embodiment, the metal portion of the zeolite Beta comprises ironin an amount ranging from 1.0 to 10.0 weight percent of the total weightof the material, with at least 60 percent of the iron present asisolated cations at the exchanged sites.

In another embodiment, the metal portion of the zeolite Beta comprisescopper in an amount ranging from 1.0 to 10.0 weight percent of the totalweight of the material.

The source of iron is typically an iron salt is chosen from ferricnitrate, ferric chloride, ferrous chloride, and ferrous sulfate.

The source of copper is typically chosen from cupric acetate, cupricchloride, cupric hydroxide, cupric nitrate and cupric sulfate.

There is also disclosed a method of making a metal containing zeoliteBeta. Generally, the present method is directed to making ametal-containing beta zeolite by first making an aqueous solutioncomprising NaOH and a source of alumina. Non-limiting examples ofsources of alumina that may be used in the present disclosure includesodium aluminate, aluminum hydroxide, alumina, aluminum nitrate, andaluminum sulfate.

Next, a source of silica is added to the solution and mixed. The sourceof silica may comprise a silica gel or silica sol, which is typicallyadded under vigorous stirring conditions. Non-limiting examples of othersources of silica that might be used include known silicates, such assilica gel, sodium silicate, and sodium metasilicate, as well ascolloidal silica, precipitated silica, silica-alumina, and the like.

Next, a source of zeolite Beta is added, typically in an amount rangingfrom about 1 to 15 weight percent, such as 10 wt. %, with respect to thesilica content of the slurry. The source of Beta zeolite is acommercially available Beta. In one embodiment, the source of zeoliteBeta are seed crystals comprising a zeolitic material having a Betaframework structure. While the mixture can be prepared by any knownmeans. In one embodiment, mixing by agitation or stirring is used. Aftermixing for about 30 minutes, a gel is formed. The mixing time can be upto 24 hours, or even up to 48 hours.

Next, the gel is heated to form a product. The duration of thecrystallization step varies depending on the desired parameters of thefinal product, such as crystal size and purity. The synthesis is haltedwhen pure zeolite Beta is formed. In one embodiment, the crystallizationstep comprises heating the gel in an autoclave at a temperature rangingfrom 100° C. to 200° C., such as 125° C., for a time ranging from 24 to200 hours, such as from 40 to 150 hours, or even 50 to 125 hours.

It is important in the commercial manufacturing of zeolite toefficiently use raw materials. In the synthesis of zeolite Beta withoutSDA, the silica utilization is of the highest importance since it is thelargest component by weight in the synthesis mixture. In commercialzeolite synthesis, silica utilization should be greater than 30%, suchas greater than 40%, or even greater than 50%. Silica utilization can becalculated by dividing the silica-to-alumina ratio (SAR) of the productto the SAR of the synthesis mixture excluding the seeding material.

Next, the crystallized material is optionally treated with at least oneprocess chosen from isolation, washing and drying. Isolation of thecrystallized product occurs using well-known techniques, such asfiltration, ultrafiltration, diafiltration, centrifugation and/ordecantation methods, wherein filtration methods can involve suctionand/or pressure filtration steps.

After the foregoing procedures of filtering, washing and drying, thecrystallized product shows a pure-phase Beta zeolite.

With respect to the optional washing steps, suitable agents which may beused include, water, alcohols, such as methanol, ethanol or propanol, ormixtures thereof. Typically, the isolated and purified zeolitic materialis washed until the pH of the effluent is in the range of from 6 to 8.

The method may comprise an additional step of removing any residualsodium from the product. This is typically done via an ion-exchangeprocess with known salts or the like, including ammonium salts of C₁,SO₄, NO₃. In one embodiment, residual sodium is removed by slurrying theproduct in a solution of a desired salt, such as NH₄NO₃, for exampleslurrying the solid at least one time in a NH₄NO₃ solution (3.6 M).

In one embodiment, the product may further subject to an ion-exchangeand/or impregnation step to increase the amount of metal or add at leastone additional metal.

In addition to the inventive method of making and the inventive Betazeolite, there is disclosed a method of using the disclosed inventiveBeta zeolite. For example, a typical exhaust gas of a diesel enginecontains from about 2 to 15 volume percent oxygen and from about 20 to500 volume parts per million nitrogen oxides (normally comprising amixture of NO and NO₂). The reduction of nitrogen oxides with ammonia toform nitrogen and H₂O can be catalyzed by metal-promoted zeolites, hencethe process is often referred to as the “selective” catalytic reduction(“SCR”) of nitrogen oxides.

Thus, there is also disclosed a method of selective catalytic reductionof nitrogen oxides in exhaust gas. In one embodiment, the methodcomprises:

-   -   at least partially contacting exhaust gases with an article        comprising a metal-containing zeolite Beta with SAR between 5        and 20, where the zeolite Beta is made without organic structure        directing agent (SDA) and the metal comprises iron and/or copper        in an amount of at least 1.0 wt %, such as an amount ranging        from 1-10 wt. %.

It is appreciated that the contacting step may be performed in thepresence of ammonia, urea or an ammonia generating compound.Non-limiting examples of ammonia generating compounds include, ammoniumcarbamate, ammonium formate, ammonium carbonate and metal-aminecomplexes. It is appreciated that any compound that is capable ofgenerating ammonia may be used in the contacting step described herein.In this embodiment, the contacting step is typically performed in thepresence of a hydrocarbon compound.

In one embodiment, the article described herein may be in the form of achanneled or honeycombed-shaped body; a packed bed; microspheres; orstructural pieces. The packed bed may comprise balls, pebbles, pellets,tablets, extrudates, other particles, or combinations thereof. Thestructural pieces may be in the form of plates or tubes. In addition,the channeled or honeycombed-shaped body or structural piece may beformed by extruding a mixture comprising the Beta zeolite.

In one embodiment, the metal-containing zeolite Beta described hereinexhibits an NO_(x) conversion of at least 40% at 200° C. for selectivecatalytic reduction with an ammonia generating compound after exposureto 700° C. for 16 h in the presence of up to 10 volume % of water vapor.

Thus, in one embodiment there is also disclosed a method of SCR ofnitrogen oxides in exhaust gases which comprises at least partiallycontacting an exhaust gas with the Beta zeolite disclosed herein. Inorder to reduce the emissions of nitrogen oxides various exhaust gases,ammonia is typically added to the gaseous stream containing the nitrogenoxides. In one embodiment of the present invention, ammonia is used toallow the gaseous stream, when contacted with the inventive Beta zeoliteat elevated temperatures, to catalyze the reduction of nitrogen oxides.

In one embodiment, a urea solution may be used to provide the ammonia tothe gaseous stream. This is particularly true when used in automotiveexhaust treatment applications and stationary NO_(x) reductionapplications.

Non-limiting examples of the types of exhaust gases that may be treatedwith the disclosed zeolites include both automotive exhaust, from on andoff road vehicles, including diesel engines. In addition, exhaust fromstationary sources, such as power plants, stationary diesel engines, andcoal-fired plants, may be treated. Thus, there are also disclosedmethods of treating exhaust emissions, such as automotive exhaust orexhaust from stationary sources.

The Beta zeolite of the present invention may be provided in the form ofa fine powder which is admixed with or coated by a suitable refractorybinder, such as alumina, bentonite, silica, or silica-alumina, andformed into a slurry which is deposited upon a suitable refractorysubstrate. In one embodiment, the carrier substrate may have a“honeycomb” structure. Such carriers are well known in the art as havinga many fine, parallel gas flow passages extending there through.Non-limiting examples of the material used to make the honeycombstructure comprise cordierite, mullite, silicon carbide, alumina,titania, zirconia, silica, alumina-silica, alumina-zirconia, stainlesssteel, Fe—Cr—Al alloy and the combinations thereof.

In another embodiment, the Beta zeolite may be provided in discreteforms (as opposed to a coating on a substrate). Non-limiting examples ofsuch forms include pellets, tablets or particles of any other suitableshape, for use in a packed bed, for example. The Beta zeolite accordingto the present invention may also be formed into shaped pieces such asplates, tubes, or the like.

Aside from the subject matter discussed above, the present disclosureincludes a number of other exemplary features such as those explainedhereinafter. It is to be understood that both the foregoing descriptionand the following description are exemplary only.

EXAMPLES Example 1 Synthesis of Organic-Free Beta (SAR=10.3) andSubsequent Fe-Exchange to make Fe-Beta (4.0 wt % Fe, SAR=10.3)

Water, NaOH (50%) and sodium aluminate (23.5% Al₂O₃, 19.6% Na₂O) weremixed together. Silica gel (PQ Corporation) was added to the solutionand mixed vigorously for 1 hour. Finally, commercially available zeoliteBeta (Zeolyst International) in the amount of 5 wt. % with respect tothe silica content of the slurry were added to the mixture and stirredfor 30 minutes. The gel had the following molar composition:

15.0SiO₂:1.0 Al₂O₃:3.8Na₂O:259H₂O

The gel was loaded into a 45-mL Parr bomb and heated under staticconditions to 125° C. for 120 hours. After cooling, the product wasrecovered by filtration and washing. The X-ray diffraction pattern ofthe product showed pure-phase zeolite Beta.

To remove residual sodium, the solid was slurried in a 3.6 M NH₄NO₃solution and stirred at 90° C. for 2 hours. This NH₄NO₃ exchange processwas repeated twice. After filtering, washing, and drying, the finalproduct had silica-to-alumina ratio (SAR) of 10.3. The BET surface areaof the product was 665 m²/g and micropore volume was 0.23 cc/g.

The sample was then ion-exchanged with a FeSO₄ solution at 70° C. for 2hours. After filtering, washing and drying, the Fe-Beta productcontained 4.0 wt. % Fe.

After steaming at 700° C. for 16 hours in 10% steam/air, the BET surfacearea of the material was 461 m²/g and the micropore volume was 0.15cc/g.

Example 2 (Comparable) Fe-Beta (1.0 wt. % Fe, SAR=25) by AqueousIon-Exchange

Commercial Beta zeolite from Zeolyst (CP 814E, SAR=25) was ion-exchangedwith FeCl₂ solution at 80° C. for 2 hours. After filtering, washing anddrying, the Fe-Beta product had 1.0 wt. % Fe, a BET surface area of 693m²/g and a micropore volume of 0.19 cc/g.

After steaming at 700° C. for 16 hours in 10% steam/air, the surfacearea of the material was 590 m²/g and the micropore volume was 0.16cc/g.

Example 3 Synthesis of Organic-Free Beta

Water, NaOH (50%) and sodium aluminate (23.5% Al₂O₃) were mixedtogether. Silica gel (PQ Corporation) was added to the solution andmixed vigorously for 1 hour. Finally, commercially available zeoliteBeta (Zeolyst International) in the amount of 10 wt. % with respect tothe silica content of the slurry were added to the mixture and stirredfor 24 hours. The gel had the following molar composition.

32.8SiO₂:1.0 Al₂O₃:9.2Na₂O:794H₂O

The gel was loaded into a 2-liter Parr autoclave and heated at 125° C.for 47 hours under static conditions. After cooling, the product wasrecovered by filtration and washing. The X-ray diffraction pattern ofthe product showed pure-phase Beta zeolite.

To remove residual sodium, the solid was slurried in a 3.6 M NH₄NO₃solution and stirred at 90° C. for 2 hours. This NH₄NO₃ exchange processwas repeated twice. The properties of the material after filtering,washing, and drying are listed in Table 1.

The sample was then ion-exchanged with a FeSO₄ solution at 70° C. for 2hours, followed by filtering, washing and drying. The Fe content,surface area and micropore volume are listed in Table 2.

Example 4 Synthesis of Organic-Free Beta

Water, NaOH (50%) and sodium aluminate (23.5% Al₂O₃) were mixedtogether. Silica gel (PQ Corporation) was added to the solution andmixed vigorously for 1 hour. Finally, commercially available zeoliteBeta (Zeolyst International) in the amount of 10 wt. % with respect tothe silica content of the slurry were added to the mixture and stirredfor 24 hours. The gel had the following molar composition.

22.0SiO₂:1.0Al₂O₃:6.2Na₂O:337H₂O

The gel was loaded into a 2-liter Parr autoclave and heated at 125° C.for 52 hours while stirring at 100 rpm. After cooling, the product wasrecovered by filtration and washing. The X-ray diffraction pattern ofthe product showed pure-phase Beta zeolite.

To remove residual sodium, the solid was slurried in a 3.6 M NH₄NO₃solution and stirred at 90° C. for 2 hours. This NH₄NO₃ exchange processwas repeated twice. The properties of the material after filtering,washing, and drying are listed in Table 1.

The sample was then ion-exchanged with a FeSO₄ solution at 70° C. for 2hours, followed by filtering, washing and drying. The Fe content,surface area and micropore volume are listed in Table 2.

The NH₄-exchanged Beta from this example was also ion-exchanged toobtain different Fe-loadings using FeSO₄ solutions at 20° C. for 2hours, followed by filtering, washing and drying.

The NH₄-exchanged Beta from this example was also ion-exchanged withcopper nitrate to obtain a sample containing 4.8% Cu.

TABLE 1 Properties of NH₄-exchanged organic-free Beta samples Example 12 3 4 Crystal size (microns) 0.4-0.6 0.1 0.1-0.3 0.2-0.5 SAR (SiO₂/Al₂O₃molar ratio) 10.3 23 10.8 9.3 Surface Area (m²/g) 665 696 679 672Micropore Volume (cc/g) 0.23 0.18 0.23 0.23 Acidity (mmol/g) 2.1 1.0 2.12.0 Silica utilization in synthesis (%) 69 — 33 42

TABLE 2 Properties of Fe-exchanged Beta samples in fresh form and aftersteaming at 700° C. for 16 h in 10% water/air. Example 1 2 3 4 Fe (wt%)4.0 1.0 3.4 2.0 Fresh sample Surface Area (m²/g) 693 621 624 MicroporeVolume (cc/g) 0.19 0.21 0.22 Sample steamed at 700 C., 16 h, 10%water/air Surface Area (m²/g) 461 590 476 494 Micropore Volume (cc/g)0.15 0.16 0.16 0.16 Surface area retention (%) 85 77 79

Example 5 (Comparable) Fe-Mordenite (1.5 wt. % Fe, SAR=14) by AqueousIon-Exchange

Commercial mordenite zeolite from Zeolyst (SAR=14) was ion-exchangedwith FeSO₄ solution at 70° C. for 2 hours. After filtering, washing anddrying, the Fe-mordenite product had 1.5 wt. % Fe, a BET surface area of522 m²/g and a micropore volume of 0.19 cc/g.

After steaming at 700° C. for 16 hours in 10% steam/air, the surfacearea of the material was 460 m²/g and the micropore volume was 0.15cc/g.

Example 6 (Comparable) Fe—Y (1.5 wt. % Fe, SAR=5.5) by AqueousIon-Exchange

Commercial Y zeolite from Zeolyst (CBV 500, SAR=5.5) was Fe-exchanged.After filtering, washing and drying, the Fe—Y product had 1.5 wt. % Fe,a BET surface area of 759 m²/g and a micropore volume of 0.27 cc/g.

NH₃—SCR of NO with Ferrialuminosilicate Zeolites

The activities of Fe-Beta for NO conversion using NH₃ as reductant wereevaluated in a flow-through type reactor. Powder zeolite samples werepressed and sieved to 35/70 mesh and loaded into a quartz tube reactor.The gas stream contained 500 ppm NO, 500 ppm NH₃, 5% O₂, and balance N₂.The hourly space velocity for all reactions was 60,000 h⁻¹. The reactortemperature was ramped and NO conversion was determined with an infraredanalyzer at each temperature interval. FIG. 1 compares SCR of NO withNH₃ on Fe-Beta samples steamed at 700° C. for 16 hours in 10% H₂O/air.

FT-UV Spectroscopy of Fe-Containing Zeolites

UV spectra were collected at ambient temperature from 200 to 400 nm onsteamed Fe-samples after evacuation in situ at 400° C., and are shown inFIGS. 12 and 13. The spectra were deconvoluted to 5 Gaussian peakscentered at 192, 209, 228, 266 and 308 nm (+/−10 nm variation for eachpeak) with a fit accuracy of R²>0.99. Peak areas as well as peak areapercentages are shown in Table 3. The peaks centered below 300 nm areassociated with isolated Fe-species, whereas the peaks above 300 nm areassociated with oligomeric Fe-species. Fe-exchanged materials of variousFe-loadings based on Beta made in Example 4 have more than 80% of Fe asisolated Fe-sites, whereas Comparable Example 2 has 73% isolated sites.

TABLE 3 Peak integrations of the UV data from FIG. 13 Example 4 4 4 4 2Fe (wt%) 0.6 1.0 1.7 2.0 1.0 NO_(x) conversion at 19 38 55 84 28 200° C.(%) Total area 105 184 287 350 140 (KM × nm) Area Area Area Area Area(KM × (KM × (KM × (KM × (KM × Peak position nm) nm) nm) nm) nm) 192 nm 65 7 7 12 209 nm 21 40 55 87 13 228 nm 27 47 73 101 33 266 nm 33 62 97 9844 308 nm 19 31 55 57 38 Peak position Area % Area % Area % Area % Area% 192 nm 5 3 3 2 9 209 nm 20 22 19 25 9 228 nm 26 25 25 29 24 266 nm 3133 34 28 31 308 nm 18 17 19 16 27 Percent isolated 82 83 81 84 73 Fe(<300 nm)

The NH₃—SCR activity correlates well with the peak area of the UV peakscentered at 209 and 228 nm, i.e. the larger those peak areas, the moreactive the material is. For example, Beta in Example 4 with 1.0% Fe haspeak areas of 40 and 47 area units (KM units×nm) at 209 and 228 nm,respectively, and 38% NOx conversion at 200° C. Beta in Example 4 with1.7% Fe has peak areas of 55 and 73 KM units×nm at 209 and 228 nm,respectively, and a NOx conversion of 55%. Zeolite Beta in Example 4with 2.0% Fe has peak areas of 87 and 101 KM units×nm at 209 and 228 nm,respectively, and a NOx conversion of 84%. The increase in the NOxconversion occurs simultaneously with the increase in peak areas at 209and 228 nm suggesting that these bands are associated with the activesites for NH₃—SCR in these materials.

Unless otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention.

Other embodiments of the invention will be apparent to those skilled inthe art from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

1. An organic-free, metal-containing zeolite Beta with molarsilica-to-alumina ratio (SAR) ranging from 5 to 20, wherein said metalcomprises iron and/or copper in an amount of at least 1.0 wt. %.
 2. Theorganic-free, metal-containing zeolite Beta of claim 1, with the provisothat if said zeolite Beta contains any organic structure directing agent(SDA) within the pore structure it originated from the seed materialduring synthesis.
 3. The metal-containing zeolite Beta of claim 1,wherein said SAR ranges from 5 to
 11. 4. The metal-containing zeoliteBeta of claim 1, wherein said iron or copper is introduced byliquid-phase or solid ion-exchange, impregnation, or incorporated bydirect-synthesis.
 5. The metal-containing zeolite Beta of claim 1,wherein said metal comprises iron in an amount ranging from 1.0 to 10wt. %.
 6. The metal-containing zeolite Beta of claim 1, wherein saidmetal comprises iron in an amount ranging from 2.0 to 10 wt. %.
 7. Themetal-containing zeolite Beta of claim 1, wherein said metal comprisesiron in an amount ranging from 3.0 to 8.0 wt. %.
 8. The metal-containingzeolite Beta of claim 4, where at least 60% of the iron is present asisolated cation at the exchanged site.
 9. The metal-containing zeoliteBeta of claim 1, where said metal comprises copper in an amount rangingfrom 1.0 to 10 wt. %.
 10. The metal-containing zeolite Beta of claim 1,wherein said metal comprises copper in an amount ranging from 2.0 to 10wt. %.
 11. The metal-containing zeolite Beta of claim 1, which exhibitsan NO_(x) conversion of at least 40% at 200° C. for selective catalyticreduction with an ammonia generating compound after exposure to 700° C.for 16 h in the presence of up to 10 volume % of water vapor.
 12. Themetal-containing zeolite Beta of claim 1, which exhibits an NO_(x)conversion of at least 60% at 200° C. for selective catalytic reductionwith an ammonia generating compound after exposure to 700° C. for 16 hin the presence of up to 10 volume % of water vapor.
 13. A method ofselective catalytic reduction of nitrogen oxides in exhaust gas, saidmethod comprising: at least partially contacting said exhaust gases withan article comprising an organic-free, metal-containing zeolite Beta,wherein said metal comprises iron and/or copper in an amount of at least0.5 wt. %.
 14. The method of claim 13, wherein said organic-free,metal-containing zeolite Beta has a molar silica-to-alumina ratio (SAR)ranging from 5 to
 20. 15. The method of claim 14, wherein said zeoliteBeta has SAR ranging from 5 to
 11. 16. The method of claim 13, with theproviso that if said zeolite Beta contains any organic structuredirecting agent (SDA) within the pore structure it originated from theseed material during synthesis.
 17. The method of claim 13, wherein saidcontacting step is performed in the presence of ammonia, urea or anammonia generating compound.
 18. The method of claim 13, wherein saidcontacting step is performed in the presence of hydrocarbon compound.19. The method of claim 13, wherein said copper or iron is introduced byliquid-phase or solid ion-exchange, impregnation, or incorporated bydirect-synthesis.
 20. The method of claim 13, wherein said ironcomprises at least 1.0 weight percent of the total weight of saidmaterial and at least 60% of the iron is present as isolated cation atthe exchanged site.
 21. The method of claim 13, wherein said ironcomprises an amount ranging from 1.0 to 10.0 weight percent of the totalweight of said material.
 22. The method of claim 13, wherein said ironcomprises an amount ranging from 2.0 to 10.0 wt. % of the total weightof said material.
 23. The method of claim 13, wherein said ironcomprises an amount ranging from 3.0 to 8.0 wt. % of the total weight ofsaid material.
 24. The method of claim 13, wherein said copper comprisesan amount ranging from 1.0 to 10.0 wt. % of the total weight of saidmaterial.
 25. The method of claim 13, wherein said copper comprises anamount ranging from 2.0 to 10.0 wt. % of the total weight of saidmaterial.
 26. The method of claim 13, wherein said zeolite Beta hascrystal size greater than 0.1 micron.
 27. The method of claim 13,wherein said zeolite Beta has crystal size ranging from 0.2 to 5microns.
 28. The method of claim 13, wherein said article is in the formof a channeled or honeycombed-shaped body; a packed bed; microspheres;or structural pieces.
 29. The method of claim 28, wherein said packedbed comprises balls, pebbles, pellets, tablets, extrudates, otherparticles, or combinations thereof.
 30. The method of claim 28, wheresaid structural pieces are in the form of plates or tubes.
 31. Themethod of claim 28, wherein the channeled or honeycombed-shaped body orstructural piece is formed by extruding a mixture comprising the Betazeolite.
 32. A method of synthesizing zeolite Beta with molarsilica-to-alumina ratio (SAR) ranging from 5 to 20, without organicstructural directing agent (SDA), excluding any seeding materials,wherein said zeolite Beta has silica utilization of greater than 30percent from the synthesis mixture.
 33. The method of claim 32, whereinsaid zeolite Beta has silica utilization of greater than 50 percent fromthe synthesis mixture.